Process for the production of hydrogen



May 10 1938 D. c. BARDWELL ET AL 2,116,993

PROCESS FOR THE PRODUCTION OF HYDROGEN Original Filed- Sept. 25, 1950 Parma May 1o, 193s oFFi 1.1;;

PROCESS FOR THE PRODUCTION F HYDGEN Dwight C. Bardweli, Syracuse, N. Y.,

Porter, Prince George County, Va., by mesne assignments,- to Company, New York, N. Y.,

New York @riginal application' September Divided and Frank assignors, The Solvay Process a corporation of es, 1930, serial and this application March 10, 1936, Serial No. 63,040

8 Claims.

This invention relates to afprocess and apparatus for the production of. a combustible gas substantially free from hydrocarbons from a gas containing hydrocarbons. More particularly. this invention relates to a process for the production of a gas containing hydrogen and nitrogengas, by passing it in contact with refractory mahydrogen and carbon monoxide with or Withoutv terial previously heated by burning a` portion of natural gas in direct contact therewith or to incompletely burn natural gas with air or oxygen in limited amounts to produce a gas containing nitrogen. The processes heretofore proposed have not been found suitable for thepreparation by .the reaction of a. hydrocarbon gas with steam of a hydrogen `gas which is to be employed in industrial processes, such as the synthesis of ammonia, where an exceedingly high degree of purity of the gas is a requisite. synthesis process, for example, where the synthesis gases are passed over a catalyst and after removal of ammonia product, the residual un combined gases are recirculated in a cyclicsystem y into renewed contact-with the catalyst, a content of about 0.5%' of hydrocarbon in the hydrogennitrogen gasintroduced into the synthesis is substantially the upper vlimit ofj this impurity which is permissible for economic operation of the 1 process. The gaseous;produc ts from the above processes contain residual undecomposed hydroz factory for use in the 4synthesis of. ammonia therefrom.

carbon in an amount which renders them unsatis- It is an object of this invention to provide `a processv for Ythe thermal decomposition in the high temperature presence ofv .steam of the hydrocarbon content of the same in which the requisite for the production of a gas substantially free from and maintained in an efficient manner. ,It is a further objectof this invention to .provide an efficient process for the production of a hydrogennitrogen gas suitable for catalytic synthesis of ammonia therefrom from a gas containing hydrocarbons. such as natural gas or water gas, produced from bituminous fuel. Other' objects of In an ammonia 'hydrocarbon may be attained (di. as me) the invention will in part be obvious and will inV part appear hereinafter.

The processes of thisv invention, more particularly described hereinafter, for the decomposition of a hydrocarbon gas comprise burning a combustible gas with preheated air `in a combustion chamber. Sensible heat contained in the hot products of combustion' is recovered and transferred, a portion to av mixture of a hydrocarbon gas and steam and another portion to air to preheat the same by passing the methane and steam and the air vertically .upwards through zones of increasing temperature in heat regenerators containing refractory material. The thus heated hydrocarbon-steam mixture, in which a large portion -of the hydrocarbon has been decomposed during its passage in contact with the hotter portions of refractory material in the regenerator,

and the preheated air are mixed and as a result of incomplete combustion of a portion of the hydrocarbon gas, the mixture is heated to a high temperature of about carbon 'is substantially completely decomposed by means of the steam and oxygen and a gaseous product formed containing nitrogen, hydrogen and carbon monoxide and substantially free from hydrocarbons. The amount of. air employed is preferably regulated toproduce a gaseous product containing about'one volume of nitrogen to every three volumes of hydrogen and carbon monoxide taken together. Sensible. heat contained in the hot products of the reaction is recovered by passing them vertically downwards through a zone of ydecreasing temperature `in a heat regenerator containing refractory material and the heat thus recovered is transferred to air which is subsequently employed for burning a'combustible gas to produce heat required for the reaction of a subsequent 'portion of hydrocarbon gas, steam and air. Thus, in the described process, the flow of the gases before, during and after the reaction, takes place substantially IWholly in a vertical direction.

For a fuller understanding o f the nature and objects of this invention, reference should be had -to the following detailed description taken in conjunction with the laccompanying drawing.

,In the drawing, Fig. l illustrates a process for the production of a hydrogen gas from bituminous fuel; and Fig. 2 illustratesr a of a `hydrogen gas by hydrocarbon gas. such as natural gas.

Referring now to Fig. 1 of the drawing, the numeral l indicates a'water'gas generator of well l500 C. whereby the hydrol thedecomposition of.` a Y.

known design provided with a pipe 2 entering the bottom of the generator whereby air from a pipe 3 may be blasted throughfthe bed of fuel and the hot blast gases taken off from the topof the generator through a pipe 4 and in another period of operation steam from the pipe 5 niay be introduced into the bottom of the fuel bed and the water gas generated by reactiony of the steam in the fuel bed taken ofi from the top of the generator through a pipe 6. The generator is also provided with a pipe I for introducing steam into the top of the generator-and pipe 8 for removing the gaseous products from the bottom of the generator. Numerals y9, I0 and II indicate three heatregenerators containing a refractory material I2. Refractory material I2 may consist of bricks laid in the regenerators as a checker work. Referring again to Fig. 1, pipe 4 enters regenerator 9 above the packing contained therein. The

top portion of this regenerator serves as a combustion chamber I9. A pipe 20 leads from combustion chamber I9 to the tops of regenerators I0 and II. Pipes Ii and 8 communicate with a pipe 2l which leads to the bottom of regenerator I0. The bottom of. regenerator I I) is in communication with waste heat boiler 22, pipe 23, and stack 24 by means of pipe 25. A pipe 26 communicates between the bottom of regenerator II and stack 21 and pipe 28 communicates with the bottom of regenerator II. Pipes 29 and 39 communicate with the bottom of regenerator 9. Valves for controlling the ilow of gases in the system are indicated.

In employing the apparatus shown in Fig. 1 for the production of a hydrogen gas substantially free from hydrocarbons from bituminous fuel, such as bituminous coal, a bed of hot fuel in gas generator I is blasted by air admitted to the bottom of the fuel bed from pipe 3 through pipe 2 and the hot blast gases passed through pipe 4 into combustion chamber I9. Air from pipe 30 is passed through regenerator 9 which has been previously heated by the hot gases produced by a precedinggas-,making operation in the manner described below andany combustible gas in the blast gases from pipel is burned in combustion chamber I9 and the hot products of combustion passed through pipe 2,0 and are divided and a portion passed through regenerator I0 and anf other portion passed through regenerator II where they give up sensible heat to the refractory material thereinI and serve to heat the material to a high temperature. The gases from regenerator Ill, after being employed in waste heat boiler 22 for the production of steam, are vented through pipe 23 andl stack 24 to the atmosphere. The hot gases from regenerator II are vented to the atmosphere through pipe 26 and stack 21. When the fuel bed in generator I has been heated to a temperature at which it will decompose steam to form water gas, the air blast from pipe 3 is shut oi and steam is admitted from pipe 5 through pipe 2. tothe bottom of the fuel bed in generator I where it is decomposed by means of the highly heated fuel with the production of water gas which is taken off from the top of the generator through pipe 6 and passed through pipe 2l to the bottom of and through regenerator I9 where it is highly heated by extraction of heat from the refractory material. Simultaneously with this gas-making step, an oxygen-containing gas, preferably air from pipe 2B, is passed through regenerator II. The water gas which has been heated in regenerator I0 and contains hydrocarbons, together with water vapor which was undecomposed `in its passage through the bed of fuel in generator I, and the preheated air from gne`rator I I, are mixed in the space above the packing material I2 and in combustion chamber I9, and a portion of the gas from regenerator I0 is burned by means of the oxygen. A combustion temperature of above about 1300o C., and preferably of about 1500 C. is maintained which induces a reaction between the hydrocarbons and steam to form carbon monoxide and hydrogen.

The quantity of air employed is limited to an amount which will produce a gas containing about one volume of nitrogen to every three volumes of hydrogen and carbon monoxide. 'lhe hot gases from the reaction between the water gas, steam and air pass from combustion chamber I9 through regenerator 9 to pipe 29 whence they are conducted to a gas holder or to ltreatment in any desired manner for the conversion of their carbon ymonoxide content to hydrogen and carbon dioxide by means of steam in the presence of a catalyst. As the operation in gas producer I continues, the passage of steam upwardly through the fuel bed may be discontinued and steam admitted to the top of the generator from pipe 'I and passed downwardly from the fuel bed and thence through pipes 8 and 2l to regenerator I0 where it is preheated prior to the treatment with preheated air as described. When the temperature of-regenerators I0 or II falls to a point at which the combustion temperature in chamber I9 is below about 1300 C. and a hydrocarbon-free gas is no longer satisfactorily produced, or when the temperature of the fuel bed in gas producerv I decreases to a point at which the gas generator is no longer operating efficiently, the introduction of steam to the bed of fuel is discontinued and the fuel bed blasted withair from pipe 3 andthe blast gases burned in combustion chamber I9 by means of air from pipe 39 preheated in regenerator 9 in the manner above described.

In carrying out the process above described, it has been found that a nitrogen-hydrogen gas containing one volume of nitrogen to every three volumes ofvhydrogen and carbon monoxide taken together and substantially free from hydrocarbons may be prepared in a practical economic manner. By suitably preheating the air employed for the combustion of the blast gases by transfer thereto of sensible heat contained in the hydrogen-nitrogen gas from the hydrocarbon deand efciently obtained and maintained during the gas producing steps of the intermittently loperating process above described.

Fig. 2 is a diagrammatic illustratlonrof a process for the decomposition of natural gas in accordance with this invention. In that figure, 3|, 32 and 33 indicate heat regenerators containing refractory packing material corresponding to regenerators 9, I0 and II respectively of Fig. 1. The upper part of regenerator 3| above the packing Vcontained therein serves as a combustion chamber 34. A pipe 35 communicates between combustion chamber 34 and the tops of regenattacca erators 32 and 33. A pipe 36 enters the bottom of regenerator 3i and serves for conducting air to this regenerator. A pipe 3l communicating with the bottom of regenerator 3i serves as an exit ,pipe for the gas produced by the decomposition of the natural gas. A pipe 38 communicates with the bottom of combustion chamber 33 above the packing in regenerator 3l. Pipes 33 and 33 communicate with the bottom of regenerator 32 and pipes il and 33 communicate `with the bottom of regenerator 33.

In employing the apparatus shown in Fig. 2

for the decomposition of natural gas to produce a gas substantially -free from hydrocarbons, air from pipe 36 is introduced into regenerator 3i and passed through the refractory material therein which has been previously heated in the manner described below. A combustible gas, which may` for example, be natural gas, is introduced into the bottom of combustion, chamber 33 where it is burned by means of the preheated air from regenerator 3i and serves to heat the combustion chamber, and the hot products of combustion pass through pipe 33 and are divided into two portions which are passed through regenerator 32 and pipe 33 and through regenerator 33 and pipe 3i respectively to the atmosphere. By burning the combustible gas in combustion chamber 33 and passing the hot products of combustion through regenerators 33 and 33, the combustion chamber and regenerators are heated to a high temperature. The introduction oi air and gas to regenerator 3i, and combustion chamber 33 is then discontinued and a mixture oi natural gasand steam is introduced into the bottom of regenerator 33 and passed through the highly heated refractory packing material contained therein. At the same time air is introduced into the bottom of regenerator 33 and passed through the heated refractory material therein. The thus heated gases from the top of regenerators 33 and 33 are mixed and a portion of the natural. gas is burned by means oi the air and serves to raise the temperature of the remaining unburned portion of the natural gas to about 1500 C. At this combustion temperature of about i500 C. the hydrocarbons are completely decomposed with the production of hydrogen and carbon monoxide, the quantity of air being limited to an amount sufficient to produce a gas product containing about one volume of nitrogen to every three volumes of hydrogen and carbon monoxide. The reaction products from combustion chamber pass through the packing material in regenerator 3l and serve to heat it. When the temperature of regenerators 33 and 33 has fallen to a point at which the hydrocarbon is no longer adequately decomposed by reaction with the steam and oxygen, for example to a temperature at which the combustion temperature of the gases in chamber 33 is below about 1300 C., the introduction of air and natural gas and steam to regenerators 32 and 33 is discontinued and air is again introduced to regenerator 3l and combustible gas to combustion chamber 33 to again heat regenerators 32 and 33 to the desired high temperature.

Provision may be made for passing steam through regenerators 32, 33 and thence through regonerator 3i before reintroducing the air into regenerator 3i and combustible gas into combustion chamber 33 in order to prevent the possibiiity of explosions occurring at the time of changing the direction of flow of the gases therethrough. Similarly, provision may be made for introducing steam into the bottom oi regenerator 3i and passing it through this regenerator and regenerators 32 and 33 after the heating-period and prior to'a subsequent gas-making period for the same purpose. If desired, the steam and air may be preheated as a mixture of the two in one regenerator and the hydrocarbon gas separately preheated in another regenerator; Furthermore, three regenerators may be employed for the separate preheating of both of the hydrocarbon gas and air and of the steam.

Since certain changes in carrying out the above process and in the constructions set forth, which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description or shown in the accompanying drawing shall be `interpretedV as illustrative and not in a limiting sense.

It is apparent to one skilled in this art that air enriched with oxygen may be employed for the incomplete ycombustion of the hydrocarbon gas in place of air. Furthermore, if a gas free from nitrogen is desired, relatively pure oxygen may be employed for this incomplete combustion of the hydrocarbon gas. If desired, regenerators 9 or 3i or combustion chambers I3 or 33 may contain a material adapted to catalyze the reaction between a hydrocarbon and steam.

This application is a division of our copending application Serial No. 484,268, filed September 25, i930.

We claim:

1. In a process for decomposing hydrocarbons at high temperatures, the steps which comprise passing the hydrocarbons upwardly through an increasingly heated refractory mass, and then passing said gases downwardly through a decreasingly heated refractory mass. l

2. A process for producing a nitrogen-hydrogen mixture for ammonia synthesswhich comprises passing a mixture of methane and steam upwardly through `a reaction zone of gradually increasing temperatures, and then passing same.

downwardly through a reaction zone of gradually decreasing temperatures while admitting a mixture of oxygen and nitrogen to the gas mixture. l

3. A process for producing amixture of nitrogen and hydrogen suitable for the synthesis oi ammonia which comprises passing a gas containing a hydrocarbon and steam upwardly through an increasingly heated refractory mass, and then passing said gas downwardly through a decreasingly heated refractory mass and introducing a mixture of oxygen and nitrogen into said gas at a point prior to the passage of the gas downwardly in contact with the decreasingly heated refractory mass.

4i. A process for the reaction oi hydrocarbon gases with water vapor to form hydrogen and` carbon monoxide at high temperatures, which consists in passing a mixture oi hydrocarbon' gases and water vaporvertically upward through a zone of increasingly heated refractory material and subsequently vertically downward through a zone of decreasingly heated refractory titi dit

material and burning gas in the circuitbetweenj the points. of maximum temperature of the two refractory masses.

5. A process for decomposing hydrocarbons atl high temperatures which comprises preheating and partially decomposing the hydrocarbons while passing upwardly through a heated reractory mass, then completing the decomposition by passing the same in the same vertical direction in contact with morehighly heated refractory material, and recovering the sensible Vheat of the decomposed mixture by passing the latter downwardly through a relatively colder refractory mass. V 5 6. A process for decomposing hydrocarbons at high temperatures which comprises preheating and partially decomposing the hydrocarbons while passing upwardly through a heated refractory mass, then completing the decomposition by passing the same in the same vertical direction in contact with more highly heated refrac- 'tory material, while adding a mixture of oxygen and nitrogen to the gases during their decomposition, suiicient in amount to maintain substantially constant temperatures in the more highly heated reaction zone, and recovering the sensible heat of the decomposed mixture by passing the latter downwardly through a relatively Ycolder refractory mass. y

7. A process for the reaction of hydrocarbon gases with water vapor to form hydrogen and carbon monoxide at high temperatures in the presence of a refractory mass, characterized by the fact that the gases are first preheated and 5` partially react while passingl vertically upward through a. zone of increasing temperature and further react while passing vertically downward through a zone oi' decreasing temperature, and further characterized by the fact that the heating is accomplished in a region in the gas circuit between the top of the zone where at one time the reacting gases have had ascending temperatures in their upward travel, and the top of the zone where the reacting gaseshave had de 

